Knowledge of microscopic geomorphic structure is critical to understanding transport processes in porous building materials. X-ray scans were obtained on a variety of commonly used porous building materials to both qualitatively and quantitatively evaluate their pore structures. The specimens included natural materials (two sandstones and a limestone) and engineered materials (three types of concretes and a brick). Scanned images were processed to reconstruct geomorphic structures of these materials. Random walk analyses were performed on the reconstructed pore structures to estimate macroscopic transport properties (including tortuosity, specific surface and permeability). The effective porosity and permeability of these materials were also experimentally determined and compared to computed values. Calibration of the threshold pixel value used in the post-processing of X-ray images against measured effective porosity appears to be a more appropriate method of selecting this value than the typical approach, which employs selection based solely on observed histograms. The resulting permeabilities computed using a calibrated threshold pixel value compare better with the measured permeabilities. We also demonstrate that the relatively homogeneous and heterogeneous pore structures associated with the studied natural and engineered building materials, respectively, can be captured by X-ray tomography.